Millisecond Pulsed Films Unify the Mechanisms of Cellulose Fragmentation

Christoph Krumm, Jim Pfaendtner, Paul J. Dauenhauer

Research output: Contribution to journalArticlepeer-review

44 Scopus citations

Abstract

The mechanism of crystalline cellulose fragmentation has been debated between classical models proposing end-chain or intrachain scission to form short-chain (molten) anhydro-oligomer mixtures and volatile organic compounds. Models developed over the last few decades suggest global kinetics consistent with either mechanism, but validation of the chain-scission mechanism via measured reaction rates of cellulose has remained elusive. To resolve these differences, we introduce a new thermal-pulsing reactor four orders of magnitude faster than conventional thermogravimetic analysis (106 vs 102 °C/min) to measure the millisecond-resolved evolution of cellulose and its volatile products at 400-550 °C. By comparison of cellulose conversion and furan product formation kinetics, both mechanisms are shown to occur with the transition from chain-end scission to intrachain scission above 467 °C concurrent with liquid formation comprised of short-chain cellulose fragments.

Original languageEnglish (US)
Pages (from-to)3108-3114
Number of pages7
JournalChemistry of Materials
Volume28
Issue number9
DOIs
StatePublished - May 10 2016

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

Copyright:
Copyright 2016 Elsevier B.V., All rights reserved.

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